Thermal conductivity of MWCNT/epoxy composites: The effects of length,alignment and functionalization

Carbon nanotubes (CNTs) show great promise to improve composite electrical and thermal conductivity due to their exceptional high intrinsic conductance performance. In this research, long multi-walled carbon nanotubes (long-MWCNTs) and its thin sheet of entangled nanotubes were used to make composites to achieve higher electrical and thermal conductivity. Compared to short-MWCNT sheet/epoxy composites, at room temperature, long-MWCNT samples showed improved thermal conductivity up to 55 W/mK. The temperature dependence of thermal conductivity was in agreement with κ ∝ Tⁿ (n = 1.9–2.3) below 150 K and saturated around room temperature due to Umklapp scattering. Samples with the improved CNT degree of alignment by mechanically stretching can enhance the room temperature thermal conductivity to over 100 W/mK. However, functionalization of CNTs to improve the interfacial bonding resulted in damaging the CNT walls and decreasing the electrical and thermal conductivity of the composites.     

Thermal conductivity of a graphene oxide–carbon nanotube hybrid/epoxy composite

Thermally conductive graphene oxide (GO)–multi-wall carbon nanotube (MWCNT)/epoxy composite materials were fabricated by epoxy wetting. The polar functionality on the GO surface allowed the permeation of the epoxy resin due to a secondary interaction between them, which allowed the fabrication of a composite containing a high concentration of this hybrid filler. The thermal transport properties of the composites were maximized at 50 wt.% of filler due to fixed pore volume fraction in filtrated GO cake. When the total amount of filler was fixed 50 wt.% while changing the amount of MWCNTs, a maximum thermal conductivity was obtained with the addition of about 0.36 wt.% of MWCNTs in the filler. Measured thermal conductivity was higher than the predicted value based on the by Maxwell–Garnett (M–G) approximation and decreased for MWCNT concentrations above 0.4%. The increased thermal conductivity was due to the formation of 3-D heat conduction paths by the addition of MWCNTs. Too high a MWCNT concentration led to increased phonon scattering, which in turn led to decreased thermal conductivity. The measured storage modulus was higher than that of the solvent mixed composite because of the insufficient interface between the large amount of filler and the epoxy.     

Synthesis,morphology and physical properties of multi-walled carbon nanotube/biphenyl liquid crystalline epoxy composites

We have developed multi-walled carbon nanotube/liquid crystalline epoxy composites and studied the effects of incorporation carbon nanotubes (CNTs) on the morphology, thermal and mechanical properties of the composites. The CNTs are functionalized by liquid crystalline (LC) 4,4′-bis(2,3-epoxypropoxy) biphenyl (BP) epoxy resin for the ease of dispersion and the formation of long range ordered structure. The epoxy functionalized CNT (ef-CNT) were dispersed in the LC BP epoxy resin that can be thermal cured with an equivalent of 4,4′-diamino-diphenylsulfone to form composite. The curing process was monitored by polarized optical microscopy. The results indicate the LC resin was aligned along the CNTs to form fiber with dendritic structure initially then further on to obtain micro-sized spherical crystalline along with fibrous crystalline. With homogeneous dispersion and strong interaction between nanotubes and matrix, the composite containing 2.00 wt.% ef-CNT exhibits excellent thermal and mechanical properties. When the amount of ef-CNT exceeds 2.00 wt.%, vitrification stage of curing is fast reached, which lowers the degree of conversion. As compared with the neat resin, the composite containing 2.00 wt.% ef-CNT increases the glass transition temperature by 70.0 °C, the decomposition temperature by 13.8 °C, the storage modulus by 40.9%, and the microhardness by 63.3%.     

A graphite nanoplatelet/epoxy composite with high dielectric constant and high thermal conductivity

A simple strategy for the preparation of composites with high dielectric constant and thermal conductivity was developed through a typical interface design. Graphite nanoplatelets (GNPs) with a thickness of 20–50 nm are fabricated and homogeneously dispersed in the epoxy matrix. A high dielectric constant of more than 230 and a high thermal conductivity of 0.54 W/mK (a 157% increase over that of pure epoxy) could be obtained for the composites with a lower filler content of 1.892 vol.%. The dielectric constant still remains at more than 100 even in the frequency range of 10⁵–10⁶ Hz. When loaded at 2.703 vol.%, GNP/epoxy composites have a dielectric constant higher than 140 in the frequency range of 10²–10⁴ Hz and a high thermal conductivity of 0.72 W/mK, which is a 240% increase over that of pure epoxy. The high dielectric constant and low loss tangent are observed in the composite with the GNPs content of 0.949 vol.% around 10⁴ Hz. It is believed that high aspect ratio of GNPs and oxygen functional groups on their basal planes are critical issues of the constitution of a special interface region between the GNPs and epoxy matrix and the high performance of the composites.     

Mechanical,electrical, and thermal properties of graphene nanosheet/aluminum nitride composites

Graphene nanosheet (GNS)/aluminum nitride (AlN) composites were prepared by hot-pressing and effects of GNSs on their microstructural, mechanical, thermal, and electrical properties were investigated. At 1.49 vol% GNSs content, the fracture toughness (5.09 MPa m^1/2) and flexural strength (441 MPa) of the composite were significantly increased by 30.17% and 17.28%, respectively, compared to monolithic AlN. The electrical conductivity of the composites was effectively enhanced with the addition of GNSs, and showed a typical percolation behavior with a low percolation threshold of 2.50±0.4 vol%. The thermal conductivity of the composites decreased with the addition of GNSs.     

Thermomechanical and corrosion inhibition properties of graphene/epoxy ester–siloxane–urea hybrid polymer nanocomposites

The effect of graphene on the corrosion inhibition properties of a hybrid epoxy–ester–siloxane–urea polymer was investigated. The weight fraction of graphene was varied from 1 to 2 wt%. Direct current polarization (DCP) and electrochemical impedance spectroscopic (EIS) techniques were used to measure the polarization and coating resistance of the coated aluminum alloy substrate. The grapheme/hybrid polymer composite coatings showed much higher corrosion inhibition property when compared to the neat hybrid polymer coating. An increase in glass transition temperature and rubbery region modulus was also observed for composites containing 1–2 wt.% of graphene. A direct correlation between the rubbery plateau modulus of free standing composite thin films and corrosion resistance of the composite coatings was made, indicating that the corrosion protection mechanism is due to restriction of the polymer chain motion by graphene which causes a decrease in coating permeability.     

The use of Taguchi optimization in determining optimum electrophoretic conditions for the deposition of carbon nanofiber on carbon fibers for use in carbon/epoxy composites

Vapor grown carbon nanofibers (VGCNFs) were deposited on carbon fibers (CFs) using electrophoretic deposition (EPD). Composites of the resulting hybrid material (CF-VGCNF) in an epoxy matrix were fabricated by the vacuum-assisted resin transfer molding process. The electrical conductivities of the composites were significantly improved compared to those without the VGCNF reinforcement. The Taguchi method was used to optimize the EPD process conditions through the analysis of means and the analysis of variance for achieving a highly uniform deposition of carbon nanofibers. The parameters considered for optimization are: deposition time, applied voltage, concentration of VGCNF in a distilled water suspension, and the distance between anode (a carbon fabric) and cathode (a copper plate). An orthogonal array of L₉ (3⁴) was created in the statistical design of experiments. The through-thickness electrical conductivity of the composites produced using the optimum deposition conditions was more than 90 times that of carbon fiber/epoxy composites. When compared with the average electrical conductivity of the nine design experiments, the electrical conductivity of the CF-VGCNF/epoxy composite using a filler prepared under the optimum deposition conditions showed a 51% improvement.     

Grafting of epoxy chains onto graphene oxide for epoxy composites with improved mechanical and thermal properties

Epoxy composites filled with both graphene oxide (GO) and diglycidyl ether of bisphenol-A functionalized GO (DGEBA–f–GO) sheets were prepared at different filler loading levels. The correlations between surface modification, morphology, dispersion/exfoliation and interfacial interaction of sheets and the corresponding mechanical and thermal properties of the composites were systematically investigated. The surface functionalization of DGEBA layer was found to effectively improve the compatibility and dispersion of GO sheets in epoxy matrix. The tensile test indicated that the DGEBA–f–GO/epoxy composites showed higher tensile modulus and strength than either the neat epoxy or the GO/epoxy composites. For epoxy composite with 0.25 wt% DGEBA–f–GO, the tensile modulus and strength increased from 3.15 ± 0.11 to 3.56 ± 0.08 GPa (∼13%) and 52.98 ± 5.82 to 92.94 ± 5.03 MPa (∼75%), respectively, compared to the neat epoxy resin. Furthermore, enhanced quasi-static fracture toughness (K_IC) was measured in case of the surface functionalization. The GO and DGEBA–f–GO at 0.25 wt% loading produced ∼26% and ∼41% improvements in K_IC values of epoxy composites, respectively. Fracture surface analysis revealed improved interfacial interaction between DGEBA–f–GO and matrix. Moreover, increased glass transition temperature and thermal stability of the DGEBA–f–GO/epoxy composites were also observed in the dynamic mechanical properties and thermo-gravimetric analysis compared to those of the GO/epoxy composites.     

The effect of graphene dispersion on the mechanical properties of graphene/epoxy composites

The effect of dispersion state of graphene on mechanical properties of graphene/epoxy composites was investigated. The graphene sheets were exfoliated from graphite oxide (GO) via thermal reduction (thermally reduced GO, RGO). Different dispersions of RGO sheets were prepared with and without ball mill mixing. It was found that the composites with highly dispersed RGO showed higher glass transition temperature (T_g) and strength than those with poorly dispersed RGO, although no significant differences in both the tensile and flexural moduli are caused by the different dispersion levels. In particular, the T_g was increased by nearly 11 °C with the addition of 0.2 wt.% well dispersed RGO to epoxy. As expected, the highly dispersed RGO also produced one or two orders of magnitude higher electrical conductivity than the corresponding poorly dispersed RGO. Furthermore, an improved quasi-static fracture toughness (K_IC) was measured in the case of good dispersion. The poorly and highly dispersed RGO at 0.2 wt.% loading resulted in about 24% and 52% improvement in K_IC of cured epoxy thermosets, respectively. RGO sheets were observed to bridge the micro-crack and debond/delaminate during fracture process due to the poor filler/matrix and filler/filler interface, which should be the key elements of the toughening effect.     

Enhancing buckypaper conductivity through co-deposition with copper nanowires

Buckypapers, the thin sheets made from an aggregate of carbon nanotubes (CNTs), have demonstrated promising electrical and thermal conductivities. However, the high in-plane to perpendicular anisotropy makes its application as thermal interface materials difficult. In order to increase the perpendicular electrical and thermal conductivities, copper nanowires (Cu NWs) were introduced into buckypapers. The Cu NWs stuck into the empty spaces between CNTs, connected them perpendicularly, and even induced a certain perpendicular CNT alignment. The electrical conductivity increased continuously with increasing the Cu content, while the smallest anisotropy was observed at the 50 wt.% Cu filling because an in-plane Cu network formed and improved much more the in-plane conductivity above this filling. On the contrary, as CNTs are more thermally conducting than Cu, the loading of Cu NWs over 50 wt.% decreased the thermal conductivity. Our measurement showed a high perpendicular conductivity of 10.1 W/m K at the 50 wt.% loading, more than quadruple and double as compared with the ones for a pure buckypaper and the one filled with 67–75 wt.% Cu NWs.     

Effect of nanosized carbon black on the morphology,transport, and mechanical properties of rubbery epoxy and silicone composites

Three different types of nanosized carbon black (CB), Printex XE2 (CBP), Vulcan XC72, and Printex 140 U (CBU), were dispersed by mechanical mixing in rubbery epoxy (RE) and silicone to produce composites. It was found that the maximum possible loading of CB in the polymers depended on the surface area of CB. For a given loading, all three CBs produced similar improvements in the thermal conductivity of the resulting composites, but their effects on the electrical conductivity varied and ranged from insulating composites with CBU to conducting composites with CBP. CBP produced a greater improvement in the electrical conductivity than the thermal conductivity of the polymers compared to the other CBs. This was attributed to the high structure of CBP, which led to the formation of a concatenated structure within the matrix. The CB/silicone composites had a similar thermal conductivity to that of the CB/RE composites, but only the CBP/silicone composite produced at 8 wt % loading was electrically conducting. The compression and hardness properties of RE were also significantly improved with the addition of CB. However, in the case of silicone, only CBP had a considerable effect on the compression properties. © 2012 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Using a non-covalent modification to prepare a high electromagnetic interference shielding performance graphene nanosheet/water-borne polyurethane composite

We prepared flexible, lightweight, and high electromagnetic interference (EMI) shielding performance graphene nanosheet (GNS)/water-borne polyurethane (WPU) composites. WPU, with sulfonate functional groups, was used as the polymer matrix. By adsorbing the cationic surfactant (stearyl trimethyl ammonium chloride) on the surface of the GNSs (S-GNSs), restacking and aggregation of the GNSs have been efficiently suppressed, which also attracted sulfonate groups from the WPU matrix. Because of the favorable interfacial interactions arising from electrostatic attraction, the S-GNS exhibited good compatibility with the WPU matrix. Such a homogeneous dispersion contributed to the construction of an electrical conductive network. The S-GNS/WPU composite exhibited a low electrical conductivity percolation threshold and an outstanding enhanced electrical conductivity of approximately 5.1 S/m. A high EMI shielding effectiveness of approximately 32 dB was obtained by the WPU composites with contents of 5 vol.% (approximately 7.7 wt.%) S-GNSs.     

Effect of the compression molding parameters on the in-plane and through-plane conductivity of carbon nanotubes/graphite/epoxy nanocomposites as bipolar plate material for a polymer electrolyte membrane fuel cell

The main challenges for commercialization of a single-filler graphite (G) polymer-matrix composite as bipolar plates are its low electrical conductivity and flexural strength. The minimum requirements set by the US Department of Energy (DOE) are the electrical conductivity and flexural strength to be greater than 100 S/cm and 25 MPa, respectively. In this study, the electrical conductivity of a G/epoxy (EP) composite (single filler) is only 50 S/cm (in-plane conductivity) at 80 wt% G. However, flexural strength is greater than 25 MPa. Using carbon nanotubes (CNTs) as the second filler at a concentration of 5 wt% in a CNTs/G/EP nanocomposite resulted in the in-plane and through-plane electrical conductivity and flexural strength being 180 S/cm, 75 S/cm, and 45 MPa, respectively. The density of the CNTs/G/EP nanocomposite is also less than that of G/EP composite, which demonstrates that a total weight reduction is achievable.     

Synergistic improvement of thermal conductivity of thermoplastic composites with mixed boron nitride and multi-walled carbon nanotube fillers

The thermal conductivity of composites with a polyphenylene sulfide (PPS) matrix and a mixture of boron nitride (BN) power and multi-wall carbon nanotube (MWCNT) fillers was investigated. Synergistic improvement in thermal conductivity of the composite was observed due to the generation of three-dimensional thermal transfer pathways between the BN and MWCNT. The improvement strongly depended on surface treatment of the MWCNTs, such as hydrogen peroxide and acid treatments. The thermal conductivity of the composite was affected by the interaction and interfacial thermal resistance between the PPS matrix and the MWCNTs. The maximum thermal conductivity achieved was 1.74 W/m K for a composite that was pelletizable, injection moldable, and thermally conductive with low electrical conductivity and good mechanical properties.     

High thermal conductive diamond/Ag–Ti composites fabricated by low-cost cold pressing and vacuum liquid sintering techniques

Diamond/Ag–Ti composites were fabricated by a low-cost liquid sintering technique. The Ti addition can effectively improve wetting and promote penetration in composite pores during liquid sintering. The interface structure of the diamond/Ag–Ti composite was identified as Ag/TiC/Ag–Ti/diamond. A high thermal conductivity of 719 W/mK was obtained for the 50 vol.% diamond/Ag-1 at.% Ti composite. Using a bimodal mixture (60 vol.% 150 μm + 10 vol.% 50 μm diamond/Ag-2 at.% Ti composite), a low coefficient of thermal expansion of 6.3 × 10^− 6/K still with high thermal conductivity of 687 W/mK was achieved. These composites have potential applications for thermal management of high integration electronic devices.     

Enhanced thermal conductivity of low-temperature sintered borosilicate glass–AlN composites with β-Si3N4 whiskers

The effects of β-Si₃N₄ whiskers on the thermal conductivity of low-temperature sintered borosilicate glass–AlN composites were systematically investigated. The thermal conductivity of borosilicate glass–AlN ceramic composite was increased from 11.9 to 18.8 W/m K by incorporating 14 vol% β-Si₃N₄ whiskers, and high flexural strength up to 226 MPa were achieved along with low relative dielectric constant of 6.5 and dielectric loss of 0.16% at 1 MHz. Microstructure characterization and percolation model analysis indicated that thermal percolation network formation in the ceramic composites led to the high thermal conductivity. The crystallization of the borosilicate microcrystal glass also contributed to the enhancement of thermal conductivity. Such ceramic composites with low sintering temperature and high thermal conductivity might be a promising material for electronic packaging applications.     

The effect of graphene nanoplatelets on the thermal and electrical properties of aluminum nitride ceramics

The thermal conductivity (κ) of AlN (2.9 wt.% of Y₂O₃) is studied as a function of the addition of multilayer graphene (from 0 to 10 vol.%). The κ values of these composites, fabricated by spark plasma sintering (SPS), are independently analyzed for the two characteristic directions defined by the GNPs orientation within the ceramic matrix; that is to say, perpendicular and parallel to the SPS pressing axis. Conversely to other ceramic/graphene systems, AlN composites experience a reduction of κ with the graphene addition for both orientations; actually the decrease of κ for the in-plane graphene orientation results rather unusual. This behavior is conveniently reproduced when an interface thermal resistance is introduced in effective media thermal conductivity models. Also remarkable is the change in the electrical properties of AlN becoming an electrical conductor (200 S m⁻¹) for graphene contents above 5 vol.%.     

Improving the thermal conductivity and shape-stabilization of phase change materials using nanographite additives

Improvements in the thermal conductivity and shape-stability of paraffin phase change materials (PCMs) by adding exfoliated graphite nanoplatelets (xGnP) or graphene were compared. The composite PCMs were fabricated by mixing paraffin with xGnP or graphene in hot toluene, followed by solvent evaporation and vacuum drying. A larger increase in thermal conductivity was observed for paraffin/xGnP, with a 10 wt.% xGnP loading producing a more than 10-fold increase. Graphene shows a lower electrical percolation threshold and offers a much larger increase in the electrical conductivity of paraffin than xGnP. However, its thermal conductivity increase is much lower. Despite the excellent thermal conductivity of single-flake graphene, the large density of nanointerfaces due to the small size of the graphene flakes significantly impedes heat transfer. We also found that graphene is much more effective than xGnP as a shape-stabilizing filler. At 2 wt.% graphene loading, paraffin maintains its shape up to 185.2 °C, well above the operating temperature range of paraffin PCMs, while the paraffin/xGnP counterpart is shape-stable up to 67.0 °C only. Small amounts of graphene and xGnP can be used in combination as a low-cost and effective improver for both the heat diffusion and shape-stabilization of paraffin PCMs.     

Microstructure and thermophysical properties of B4C/graphite composites containing substitutional boron

B₄C/graphite composites (BGC) containing substitutional boron were fabricated by pressureless sintering of powder mixtures of petroleum coke, coal tar pitch and B₄C. After sintering at 900 °C and graphitizing at 2200 °C, the microstructure of BGC was characterized by SEM, TEM, XRD, Raman spectroscopy and optical microscopy. XPS measurements revealed the formation of BC₃, and the matrix carbon contained around 6 wt.% substitutional boron. The thermal conductivity of the BGC at room temperature is 52.7 W/m K and the flexural strength is up to 35.1 MPa. The bulk density and electrical resistivity are 1.72 g/cm³ and 13.4 μΩ m, respectively. The correlation between microstructure and properties was investigated. The results showed that the microstructure improvement of the BGC has obvious effect on the thermal conductivity, flexural strength, and electrical resistivity.     

Diluent filler particle size effect for thermal stability of epoxy type resin

Epoxy resin is used as a material for electrical and electronics molding in various forms but its thermal conductivity must be controlled with various additives on account of its lower conductivity than metal or ceramics. Silicon dioxide (SiO₂) and silica were selected as the reinforcement and diluent filler for epoxy resins, respectively. The optimum amount of reinforcement filler, SiO₂, was 50 wt%. The thermal properties and thermal stability were observed according to silica ratio and particle size. An epoxy modified with a polyamide type hardener showed superior thermal conductivity to that modified with a cyclo-aliphatic amine type hardener. The thermal conductivity increased with increasing silica ratio and particle size. The thermal stability evaluation based on the particle size of silica was in the order of 14/18 mesh (1.00–1.16 mm) > 8/10 mesh (1.65–2.36 mm) > 28/35 mesh (0.42–0.59 mm). The optimum silica size of the diluent filler was 14/18 mesh (1.00–1.16 mm). An epoxy type resin transformer with excellent thermal properties and thermal stability could be designed when the mixing weight of epoxy resin was equal to that of the hardener.